Polyesters prepared from hydroxyarylthio anhydrides

ABSTRACT

NOVEL COMPOUNDS OF THE FORMULA:   (R)D-A(-OH)-S-(CY2)E-C(-Y2)&lt;(-C(-Y)(-Y1)-CO-Z-CO-)   WHEREIN E IS FROM ZERO TO ONE AND D IS FROM ZERO TO ABOUT SIX, PROVIDED THAT WHEN E IS ZERO, Y1 IS HYDROGEN; AND THAT WHEN E IS ONE, Y2 IS HYDROGEN; Y, Y1 AND Y2 ARE OF ZERO TO ABOUT 20 CARBON ATOMS AND ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL, ALKARYL, ARALKYL, HYDROGEN, CYANO, AND HALOGEN; Z IS SELECTED FROM THE GROUP CONSISTING OF -NH, -0-, -S- AND -CH=CH-; A IS ARYL OF SIX TO 18 CARBON ATOMS; AND R IS OF ZERO TO ABOUT 20 CARBON ATOMS AND IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL, ALKARYL, ARALKYL, CARBALKOXY, CARBARYOXY, ALKOXY, ARYLOXY, ALKYLTHIO, ARYLTHIO, HYDROXY, MERCAPTO, CYANO, CARBOXY AND HALOGEN. SAID COMPOUNDS HAVE UTILITY AS POLYMER ADDITIVES. NOVEL POLYESTER DERIVATES OF THE HYDROXYARYLTIO SUCCINIC ANHYDRIDE AND THIOANHYDRIDE COMPOUNDS AND A PROCESS FOR PREPARING SAID POLYESTER.

States Patent 7 Claims ABSTRACT OF DISCLOSURE Novel compounds of theformula:

wherein e is from zero to one and d is from zero to about six, providedthat when e is zero, Y is hydrogen; and that when e is one, Y ishydrogen; Y, Y and Y are of zero to about carbon atoms and areindependently selected from the group consisting of alkyl, aryl,alkaryl, aralkyl, hydrogen, cyano, and halogen; Z is selected from thegroup consisting of NH, -O-, -S and CH =CH-; A is aryl of six to 18carbon atoms; and R is 'of zero to about 20 carbon atoms and is selectedfrom the group consisting of alkyl, aryl, alkaryl, aralkyl, carbalkoxy,carbaryloxy, alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto,cyano, carboxy and halogen. Said compounds have utility as polymer ad-"ditives. Novelpolyester derivatives of the hydroxyarylthio succinicanhydride and thioanhydride compounds and a process for preparing saidpolyesters.

This is a division of application Ser. No. 749,952, filed Aug. 5, 19 68.and now abandoned,

This invention relates to novel hydroxyarylthio compounds and a processfor preparing said compounds by the. reaction of mercaptophenols withreactive unsaturated compounds. p

i The addition of mercaptans to olefins is well known. This reactio'nisdescribed by E. Emmet Reid in Oragnic Chemistry of Bivalent Sulfur, Vol.11, Chemical Publishing Co., New York City, 1960, pp. 29-34. Thereactive unsaturated starting compoundsof the present invention enterinto reactions with phenol. .Phenyl esters are formed by acetylation ofphenol with, for example, citraconic anhydride. Anhydrides such asmaleic anhydride react with phenol to give malein-type products such asphenolmalein. As phenols are readily alkylated by olefins,mercaptophenol similarly could also .be expected to become a1kylatedbyolefins.

'Mrcaptophenol is not only a mercaptan, but it is also aphenol,and,,therefore, has both a reactive hydroxyl group and a reactivering. One-might expect the above alternate reactions to take precedentover the addition of themercaptan group to an unsaturated bond. Onecould not .predictthat-the compounds of this invention would be'producedby thereaction of a mercaptophenol and a reactive olefin.

, 3,832,329 Patented Aug. 27, 1974 "ice In accordance with the presentinvention, there are provided novel compounds of the formula:

wherein:

(a) e is from zero to one and d is from zero to about six;

(b) provided that:

(1) when e is zero, Y is hydrogen; and (2) when e is one, Y is hydrogen;

(0) Y, Y and Y are of zero to about 20 carbon atoms and areindependently selected from the group consisting of alkyl, aryl,alkaryl, aralkyl, hydrogen, cyano and halogen;

(d) Z is selected from the group consisting of NH,

(e) A is aryl of six to 18 carbon atoms; and

(f) R is of zero to about 20 carbon atoms and is selected from the groupconsisting of alkyl, aryl, aralkaryl, aralkyl, carbalkoxy, carbaryloxy,alkoxy, aryloxy, alkylthio, arylthio, hydroxy, mercapto, cyano, carboxyand halogen.

Also, in accordance with the present invention, there is provided aprocess for the preparation of the hydroxyarylthio succinic anhydride,succinimide, cyclohexenedione, and succinic thioanhydride compounds andnovel polyester derivatives of the hydroxyarylthio succinic anhydrideand thioanhydride compounds.

The following are typical of those compounds included within the scopeof the present invention:

l-ethyl-1-(4-hydroxyphenylthio) succinimidel-cyano-1-(2-hydroxyphenylthio) succinimide2-(3-hydroxyphenylthio)-5-cyelohexen-1,4-dione 1-phenyl-2-(2,3-dichloro-4-hydroxyphenylthio succinic thioanhydride2-hydroxyphenylthio) succinic thioanhydride Z-hydroxyphenylthio succinicanhydride 2hydroxyphenylthiomethylene succinic anhydride4-hydroxyphenylthiomethylene succinimide5-chloro-6-(4-hydroxyphenylthio) -2-cyclohexen-1,4-

dione 1-propyl-2- (2-hydroxynaphthylthio) succinic anhydride1-dodecy1-2- Z-hydroxyphenylthio succinic anhydride 2-(2-hydroxy-4,5,6-trimethylphenylthio 5-cyc1ohexen- 1,4-dione 1-benzyl-2-3-hydroxyphenylthio succinic thioanhydride1-tolyl-2-(4-hydroxyphenylthio succinimide 2- 3hydroxyphenylmethylene)succinic thioanhydride In the compounds of the present invention thecarbonyl groups are activating groups that promote the addition reactionof a mercaptophenol to an unsaturated carboncarbon bond.

R is preferably alkyl, aryl, hydroxy, or halogen, Y, Y and Y arepreferably hydrogen or alkyl. R, Y, Y and Y are preferably of zero toabout ten carbon atoms.

A is preferably phenyl, and insaid case, d is from zero to four.

When R, Y, Yl or Y are halo, they may be chlorine, fluorine, bromine oriodine.

The unsaturated compounds that may be used as starting materials in thepreparation of the compounds of the present invention are of thefollowing formula:

o-o= (oY,).

)l-I wherein subscript e and Z, Y, Y and Y are as hereinbeforedescribed. As indicated by the broken line, the unsaturation is at bond1 and 2 when e is equal to zero and at bond 2 and 3 when e is equal toone. These compositions include compounds such as benzoquinone, maleicanhydride, itaconic anhydride, malimide and maleic thioanhydride.

The starting mercaptophenol compounds of the present invention are ofthe formula: HS-A(R) OH; where in A, R and d are as hereinbeforedescribed. Said compounds may be prepared by methods known in the priorart or by the procedure described in copending appllcation Ser. No.597,228, filed Nov. 28, 1966, now abandoned and refiled as Ser. No.666,915, filed Sept. 11, 1967, now U.S. 3,468,961. Mercaptophenols, suchas o-mercaptophenol, p-mercaptophenol, 3,5-dimethyl Z-mercaptophenol, 4-phenyl-Z-mercaptophenol, 3-cyano-2-rnercaptophenol and4-carboxy-3-mercaptophenol, are typical starting compounds.

The following reaction illustrates the process for the preparation ofthe novel compounds of the present mvention.

Subscripts d and e, and Z, A, R, Y, Y and Y are as hereinbeforedescribed.

Although the reaction may be conducted in the absence of a solvent, itis normally conducted in the presence of a solvent. Typical solventsinclude benzene, toluene, xylene, heptane, hexane, chloroform, carbontetrachloride, chlorobenzene, dioxane, N,N-dimethylforr nam1de,N-methyl-Z-pyrrolidone, tetrahydrofuran and dimethylsulfoxide.

Although the reaction may be conducted at a temperature of about zero toabout 200 degrees centigrade, the preferred temperature is from about toabout 150 degrees centigrade.

Although the reaction may be conducted in the absence of a catalyst, thetime and temperature required to complete the reaction may generally bereduced by using a basic catalyst. A catalytic amount of about .05 moleof catalyst per mole of mercaptophenol is preferably employed. Suitablecatalysts include salts of strong bases and alcohols or weak acids,amines, quaternary amine bases and alkali or alkaline earth metals orhydroxides. Examples of catalysts are sodium methylate, sodium acetate,potassium carbonate, triethyl amine, piperidine, triethylene diamine,trimethylbenzylammonium hydroxide and sodium or magnesium and sodiumhydroxide.

The hydroxyarylthio succinic anhydrides and thioanhydrides of thepresent invention can be reacted with glycols or thioglycols to give thenovel polyesters of the present invention.

4 Said novel polyesters contain at least ne unit of the formula Y, Y YA, R and subscripts d and e fore described.

The preferred polyesters of the present invention are of the formula areas hereinbe- R and subscript d are as hereinbefore described. Typicalglycols or thioglycols that may be used as starting compounds in thepreparation of the polyesters of the present invention are as follows:diethylene glycol, ethylene glycol, a,w-dihydroxy[poly(ethyleneoxides)],l, 2-propylene glycol, 3,4-pentanediol, 1,10-decanediol, neopentyldiol,1,4-cyclohexanediol, diethanol sulfide, 1,4-diethanolbenzene,1,4-xylylenol, 1,4,5,6,7,7-hexachloro-2,3-bis(hydroxymethyl)bicyclo-(2.2.1 )-heptene-5, ethylenedithiol,hexamethylenedithiol, a,w-dimercapto(po1y(ethylenc sulfide)1,4-bis(mercaptomethyl)cyclohexane, 1,12- dodecanedithiol and his(mercaptoethyhsulfide. Also, glycols and dithiols prepared by theoxyalkylation or thioalkylation of the above compounds and compoundssuch as 4,4'-isopropylidene diphenol, resorcinol, thiobisphenol,4,4-dihydroxydiphenyl, aniline and methylamine.

In the process for the preparation of the novel hydroxyarylthiopolyesters of the present invention, the glycol or thioglycol is reactedwith the hydroxyarylthio succinic anhydride, or the correspondingdialkyl succinate, when a transesterification procedure is used, atatemperature of about 75 to about 250 degrees centigrade,for a period ofabout 3 to about 50 hours. No catalyst is required when thepolyesterification is conducted by reaction of thehydroxyarylthiosuccinic anhydride. When a transesterification procedureis used useful catalysts are paratoluenesulfonic acid, or weakly acidicor basic catalysts such as calcium acetate or antimony triox ide. f

Standard polyesterification procedures are applicable. For example, therate of esterification can be increased by hastening the elimination ofthe condensation products, ,water or alcohol. Typically this isaccomplished by passing an inert gas stream through the reaction mixtureor by maintaining the mixture under reduced pressure, Water can also beremoved as it forms by conducting the esterifi-' cation in awater-imiscible solvent, such as toluene, whereby the water is distilledoff asa component of an azeotropic distillate. The reaction is followedby periodically determining the carboxylic acid concentration or bymonitoring the water or alcohol produced during the'course of thereaction.

The c'arboxylic reagent need not be a single compound, but can becomposed of several carboxylic compounds, of which one, several, or allcan be hydroxyarylthio-sub stituted. Also the second reactant can be amixture of several glycols or dimercaptans, Typical non-phenoliccarboxylic reagents are fumaric acid, maleic anhydride, phthalicanhydride, pyromellitic anhydride, diethyl fumarate, dimethylterephthalate, dimethyl 1,4,5 ,6,7,7-hexachlorobicyclo-(2.2.1 -5-heptane-2,3-dicarboxyl ate.

A portion of the glycol or thioglycol can be replaced by trior highersubstituted polyols or polythiols to give across-linked 'polymen-Typicalpolyols are 1,1,1-trimethylolpropane, glycerol, pentaerythritol, andoxyalkylated derivatives derived from sorbitol, sucrose andphenylenediamine.

A portion of the carboxylic reagent can be replaced with unsaturatedanhydride or ester, such as those mentioned above, for example, maleicanhydride. The resulting polyester can be crosslinked via theseunsaturated bonds with a vinyl monomer such as styrene.

The phenolic polyester compositions of this invention can be convertedto epoxy derivatives by reaction with, for example, epichlorohydrin.

. The phenolic polyester compositions of this invention can be convertedto a polyester substituted with aliphatic hydroxyl groups by treatmentwith an alkylene oxide, (oxyalkylation), such as ethylene oxide orpropylene oxide. These ester polyols are useful as reagents forpreparing polyurethane polymers by reaction with diisocyanates orpolyisocyanates. Typical isocyanates are toluene diisocyanates and thephosgenated reaction products of formaldehyde and aniline.

The hydroxyarylthiosuccinic anhydrides, succinimides andsuccinicthioanhydrides of the present invention are useful whenincorporated chemically into condensation polymers as stabilizers or asproviders of hydroxy groups. The hydroxyl groups are used to chemicallyattach polymer modifiers, such as dyes, antistatic agents, hydrophobicor .hydrophilic groups, and the like.

.positionsof the present invention with carbonyl compounds, e.g.,formaldehyde or aetone, under acid conditions with or without additionalphenol present, gives carboxylic substituted bisphenol or novolakmaterials which may be esterified with long-chain alcohols to givereagents useful for imparting chemically-bound plasticization topolymers, or which may be incorporated into polycarbonates, for example,to serve as cross-linking sites. Furthermore, reaction of the compoundsof the present invention with carbonyl compounds under alkalineconditions gives methylol or resole type materials that will cure onheating.

The following examples will further illustrate specific embodiments ofthis invention. It should be understood however that these examples aregiven by way of illustration and not limitation. All temperatures are indegrees centigrade and all parts are by weight, unless otherwiseindicated.

EXAMPLE 1 To a stirred solution of 980 parts of maleic anhydride (10.1moles), 1 part of triethylenediamine and 5600 parts toluene, was added1260 parts of a-mercaptophenol (10.0 moles) over about a 15 'minuteperiod. The reaction was exothermic. After about one-half hour thereaction mixture was cooled to five degrees centigrade. From a resultingthick slurry, 1900 parts of product were obtained on filtration.Concentration of the filtrate and further filtration resulted in moreproduct. The combined product was recrystallized from toluene infractions. The first crop,

about 2040 parts, represented a 91 percent yield and "6 melted in therange of -130 degrees centrigrade. The total weight of allcrystallization fractions corresponded to a yield of 98.5 percent.Theproduct was identified as 1-(2-hydroxyphenylthio) succinic anhydride.

Analysis- Calculated for C H S: Percent Phenolic hydroxyl 4. 4.47 Acidand anhydride 8.90 Anhydride 8.90 Found: i

Phenolic hydroxyl 4.40 Acid and anhydride 8.80 Anhydride 8.74

EXAMPLE 2 In a manner similar to Example 1, 5 parts of benzoquinone werereacted with 11.6 parts of o-mercaptophenol. About 7.4 parts of productwere obtained. The product, having a melting point of 121-122 degreescentigrade, was identified as 5-(2-hydroxyphenylthio)-2-cyclohexen-1,4-dione.

Analysz's Calculated for G i-1 0 8: C, 61.52 percent; H, 4.30

percent; S, 13.69 percent; OH, 7.24 percent. Found: C, 61.43 percent; H.4.34 percent; S, 13.4

percent; OH, 7.38 percent.

EXAMPLE 3 In a manner similar to Example 1, 2,4-di-t'butyl-6-mercaptophenol was reacted with maleic anhydride. The product, having amelting point of 137-139 degrees centigrade, was identified as1-(2-hydroxy-3,5-di-t-butylphenylthio) succinic anhydride.

Analysis- Calculated for C H O S: C, 53.56 percent; H, 3.60

percent; S, 14.30 percent; OH, 7.57 percent. Found: C, 53.55 percent; H,3.44 percent; S, 14.2

percent; OH, 7.45 percent.

EXAMPLE 4 To a solution of about 25 parts of tetrahydrofuran and 9.7parts of maleimide, were added 12.6 parts of o-mercaptophenol during a12 minute period. The reaction mixture was maintained below about 50degrees centigrade during the addtion by means of an ice bath. After thereaction mixture had stood for several days, the tetrahydrofuran wasstripped under reduced pressure. The residue was crystallized frombenzene to give 14.7 parts of product. The product, identified as(Z-hydroxyphenylthio) succinimide, had a melting point of 1120-1145degrees centigrade.

Analysis- Calculated for C H O NS: S, 14.3 percent; OH,

4.48 percent. Found: S, 14.02 percent; OH, 4.4 percent.

In a similar manner and in separate experiments, ethylmaleicthioanhydride and 1-ethyl-2-methylenemaleic anhydride are reacted with3,5-dimethyl-Z-mercaptophenol to yield the following respectiveproducts: 1-ethyl-2-(2-hydroxy-4,6-dimethylphenylthio) succinicthioanhydride and 1 ethyl-2-(2-hydroxy-4,6-dimethylphenylthiomethylene)succinic anhydride.

EXAMPLE 5 To 58.3 parts of diethylene glycol were added 112 parts (0.5moles) of (Z-hydroxyphenylthio) succinic anhydride. The mixture waswarmed to a temperature of 85 degrees centigrade at which temperaturethe anhydride went into solution. The solution was heated to 180 degreescentigrade for 75 minutes during which period 6 parts of water weredistilled oif. The system was put under millimeters of reduced pressureand the heating con- .tinued. for *one hour at 190 degrees-centigradeand for three hours at 170 degrees centigrade. The resulting productwas'a golden yellow resin.

Analysis- In a similar" manner, (2-hydroxyphenylthio)succinic anhydrideis reacted with ethylenedithiol to form a poly ester.

EXAMPLE 6 A low molecular weight resole was prepared by a phenol,formaldehyde and sodium hydroxide condensation reaction. Equal amountsof said resole and the polyester of Example were stored at 85 to 95degrees centigrade for three days. The product was a golden yellow hardresin. When the resole is subjected to the same conditions, it becomes adeep red resin.

EXAMPLE 7 Analysis Milliequivalents per gram Calculated hydroxy value3.75 Foundhydroxy value 3.81

Molecular weight: 847

While there have been described various embodiments of the presentinvention, the methods and compositions described are not intended to beunderstood as limiting the scope of the invention as it is realized thatchanges therein are possible.

What is claimed is:

1. A polyester comprising at least one unit of the formula wherein (a) eis from zero to one and d is from zero to about six;

' (b) provided that:

(1) when 2 is zero, Y is hydrogen; and (2) when e is one, Y is hydrogen;

(c) Y, Y and Y are of zero to about 20 carbon atoms and areindependently selected from the group consisting of alkyl, aryl,alkaryl, aralkyl, hydrogen, cyano andhalogen;

. (d) w is selected from the group consisting of O- and (e) A is aryl ofsix to 18 carbon atoms; and

(f) R is of zero to about 20 carbon atoms and is selected from the groupconsisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio,arylthio, hydroxy, mercapto, cy no, carboxy and halogen.

2. A process for-premring the; polyester of Claim 1, comprising reactinga compound of the formula M I wherein: g g .1

(a) e is from zero to one and d is from zero to'abou't Six; G

'(b) provided that:

( 1) when e is zero, Y is hydrogen; and (2) when e is one, Y ishydrogen;

(c) Y, Y and Y are of zero to about 2O carbon atoms and areindependently selected from the group consisting of alkyl, aryl,alkaryl, aralkyl, hydrogen, cyano and halogen;

(d) Z is selected from the group consisting of --O and (e) A is aryl ofsix to 18 carbon atoms; and

(f) R is of zero to about 20 carbon atoms and is selected from the groupconsisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio,arylthio, hydroxy, mercapto, cyano, carboxy and halo I V with a glycolor thioglycol at a temperature of about 75 degrees centigrade to about250 degrees centigrade.

3. A polyester according to the processof Claimv 2 of the formula:

wherein R is selected from the group consisting of alkyl, aryl, hydroxyand halogen and d is from zero to six.

5. The polyester of Claim 4 wherein d is 0.

6. A polyester of Claim 1 wherein:

(a) e is from zero to one and d is from zero" to about SIX;

(b) provided that:

( 1) When e is zero, Y is hydrogen; mm (2) when e is one, Y is hydrogen;

(c) Y, Y and Y are of zero to about 20 carbon atoms and areindependently selected from the group consisting of alkyl, aryl,alkaryl, aralkyl, hydrogen, cyano and halogen;

(d) w is 0;

(e) A is aryl of six to 18 carbon atoms; and

(f) R is of zero to about 20 carbon atoms and is selected from the groupconsisting of alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkylthio,arylthio, hydroxy, mercapto, carboxy and halogen.

9 10 7. A process for preparing the polyester of Claim 6, (d) Zis O;comprising reacting a compound of the formula (e) A is aryl of six to18' carbon atoms; and

O (f) R is of zero to about 20 carbon atoms and is selected II I fromthe group consisting of alkyl, aryl, alkaryl,

5 aralkyl, alkoxy, aryloxy, alkylthio, arylthio, hydroxy,

l mercapto, carboxy and halo with a glycol or thio-glycol.

c CY esA R II 2) )d References Cited Y UNITED STATES PATENTS wherein: 10(a) e is from zero to one and d is from zero to a out 3 210,37 19 5smith 2 3 5 3,472,879 10/1969 Isard et a1 260-346.2 provlded thatI3,664,986 5/1972 MacDonald 260-78 R (1) when e zero, Y is hydrogen; and(2) w 8 is Y2 is y g 15 LESTER L. LEE, Primary Examiner (c) Y, Y and Yare of zero to about carbon atoms and are independently selected fromthe group con- US. Cl. X.R.

sisting of alkyl, aryl, alkaryl, aralkyl, hydrogen, cyano 260-47 R, 50,53 R, NK, 470 and halogen;

UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION I Patent No. 3Dated August 7 97'+ fl Emi l J. Geering and Norman W. Dachs It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

l" Column 1 line 53 "Oragnic" should read --0rganic--. Column 3, lines70-71 "magnesium and" should read --'-magnesium metal and--. I Column 9,line 7, that part of the Formula reading -S--A-(R) should read -S-A-(R)Signed and sealed this 21st day of January 1975.

(SEAL) Attest:

MCCOY n. GIBSON JR. c. MARSHALL DANN Attesting Off cer Commissioner ofPatents

